Glass frit of diopside crystal precursors

ABSTRACT

A process for producing feldspathic sanitary ware and the end product are disclosed in which a fluxing amount of a glass frit is used in the ceramic slip used to cast the sanitary ware. The frit contains both deflocculent oxides and flocculent alkaline earths which are leachable from the frit when it is placed in the ceramic slip. The deflocculent oxides counterbalance the effect of the flocculent alkaline earths to the extent they are respectively leached from the frit upon dispersal in a ceramic slip and maintain the slip at a workable viscosity. Upon casting and firing the slip, the present frit precipitates fine crystals of diopside having an average particle size of less than one micron which are particularly useful in lowering the firing temperature of feldspathic bodies by promoting the required degree of vitrification at lower temperatures than heretofore possible.

This application is a continuation-in-part of copending U.S. patentapplication, Ser. No. 188,919, filed Sept. 19, 1980 now U.S. Pat. No.4,337,316.

BACKGROUND AND FIELD OF THE INVENTION

Sanitary-ware fixtures, i.e., toilet bowls, lavatories and the like,particularly the former, are constructed of a glazed, highly vitrified,feldspathic body.

The body is usually formed by the well-known method of slip casting,carefully and slowly dried, glazed and fired to vitrification in atunnel kiln at a temperature equivalent of Seger pyrometric cone 9 to10. The body is normally referred to as "feldspathic" indicating that asubstantial proportion of the mineral content of the slip is feldspar.However, nowadays feldspathic sand or nepheline syenite can beoptionally used as a partial or complete replacement for the feldsparwithout changing this generic description.

Ideally, and as will be described in more detail hereinafter, thecasting slip, as well as the final, fired, vitrified body, must meetcertain rigid, rheological and physical property standards.

For example, the viscosity, specific gravity and stability of thecasting slip should ideally remain constant over appreciable periods oftime as these factors are all critical from the standpoint of castingbodies having desired wall thicknesses, drying shrinkage, etc.

The fired body, ideally, will be completely vitrified, have highstrength, with minimum, though uniform, shrinkage on firing.

In an effort to either, or both, speed the firing operation and to lowerthe firing temperature, any number of body additives have beenexperimented with. For example, many fluxing materials have been triedto speed the body vitrification process, with varying degrees ofsuccess. However, such fluxes have generally created more problems thanthey have solved.

That is, speeding up the vitrification process poses no major problem,in and of itself; but slip instability, excessive shrinkage or warpageon drying or firing, lower strength, short vitrification range, etc.,have usually accompanied the utilization of conventional body fluxesused heretofore. By way of explanation, "short vitrification range"refers to the temperature spread, within a commercial kiln, over whichthe required degree of vitrification will both occur and be sustainedwithout slumping and/or crystallization (devitrification).

Therefore, while a vitrification range would be of little or nosignificance in a small test bar, fired under carefully controlledlaboratory conditions, it is vital to successful manufacture ofsanitary-ware products on a commercial scale in a continuous productiontunnel kiln. Thus, if a sanitary-ware body reaches vitrification atprecisely cone 10 down, while at cone 9 it is not vitrified, whereas atcone 11 it has begun to slump, the production problems become readilyapparent because there is no practical way to achieve temperaturecontrol at precisely cone 10 throughout the cross section of the firingzone of a production kiln.

A related problem in casting sanitary ware from a ceramic slip in whicha glass frit serves as a flux is that the frit tends to be somewhatsoluble. Components leached from the frit, notably the alkaline earths,act as flocculents and can sufficiently raise the viscosity of the slipto make it unworkable. In fact, some slips may even virtually solidify.Moreover, this flocculation to an unworkable viscosity can often takeplace in a relatively short time. Also, sintering of the cast ceramicslip leaves a certain amount of unreacted alkaline earth in the sinteredproduct. This likewise has an undesirable flocculating effect on theslip.

The field of this invention deals primarily with the production ofsanitary-ware body additives designed to lower the production firingtemperature of a sanitary-ware body, while at the same time preservingall the required characteristics of said body in both the slip stage, aswell as in the final, fired product. Further, the invention includes acounterbalancing of flocculents leached by the slip from fluxing fritand a resulting maintenance of a workable viscosity of the slip.

The utilization of either wollastonite (CaO.SiO₂) or diopside(CaO.MgO.2SiO₂) as an additive for ceramic bodies is disclosed by H. G.Kurczyk in a paper entitled, "Synthetic Diopside and SyntheticWollastonite--New Raw Materials for Ceramics", from the Proceedings ofthe 3rd CIMTEC, 3rd International Meeting on Modern CeramicsTechnologies at Rimini, Italy, May 27-31, 1976.

Kurczyk discloses the possibility of synthesis of diopside by any numberof means, including synthesis by solid-state reaction, crystallizationfrom a molten bath, sintering, etc. Kurczyk's preferred methodapparently is the formation of diopside from dolomite and ground quartzin the appropriate molecular ration by hydrothermal pretreatment andcalcination.

However, diopside produced by sintering, from the standpoint ofadaptability to ceramic bodies, has a number of drawbacks. First, thesintering process utilizes a rotary kiln operation similar to that usedfor the manufacture of portland cement clinker. As is well known, it isexceedingly difficult to control the firing temperature in a rotary kilnwith any degree of precision, wherein variations in temperature maypromote either a "soft burn", resulting in a high percentage ofunreacted material, or cause a partially molten bath which solidifiesupon discharge from the sintering zone, resulting in the formation of anon-uniform, heavy, slag-type coating on the calciner walls withattendant undesirable interruptions in the overall operation.

Furthermore, the diopside produced by the method disclosed by Kurczyk isrelatively large grained (10 to 30 microns) which tends to reduce itseffectiveness in lowering the firing temperature of a sanitary-ware bodyand, as is well known, the diopside mineral crystal tends to beextremely hard and tough, thereby making it most difficult to mill andgrind to a particle size small enough to be effectively dispersedthroughout a sanitary-ware body slip.

It has been found however that, if the molten bath which Kurczyk foundto be undesirable, is deliberately created under controlled conditions,followed by the novel processing steps hereinafter set forth, a moreeconomically produced, superior form of diopside is achieved, whicheliminates all the disadvantages of Kurczyk, while providing a number ofadditional improvements thereover.

OBJECTS

It is therefore an object of this invention to provide a new andimproved crystalline form of diopside.

It is another object of this invention to provide a relatively lowtemperature glass matrix from which fine grained dioside crystals may beformed upon reheating said glass to its crystallization temperature.

It is yet another object of this invention to provide diopsideprecursors in glass solution in a relatively low melting temperatureglass, which may be readily incorporated into a ceramic body, and whichglass, upon firing of the body, will precipitate at least some finegrained crystalline diopside, uniformly dispersed and formed in situthroughout said body.

It is yet another object of this invention to provide a vitreous sourceof fine grained diopside crystals which can be easily and readily milledto a sufficient fineness for incorporation into a feldspathic ceramicbody.

It is another object to achieve a process for manufacturing therelatively low temperature glass of this invention.

It is a further object to counteract flocculents leached by a slip fromglass and prevent their increasing the viscosity of the slip tounworkable values.

And finally, it is an object to provide a new and improved,sanitary-ware body, as well as provide the process for achieving same.

SUMMARY OF THE INVENTION

The present invention reduces the firing temperatures of vitreous andsemi-vitreous bodies comprising feldspathic materials, while maintaininga suitable firing range and other physical properties of such material.As a result, there is substantial fuel savings with increasedproductivity. By substantially balancing the deflocculent oxides andflocculent alkaline earth extractabilities from the glass added to aslip, its viscosity can be maintained within workable limits.

In one form of the invention, the glass hereof in the form of a finelyground frit is mixed with the ceramic material to be fired to form afeldspathic body. The frit contains in solution quantities of the oxidescontained in diopside, namely MgO, CaO, and SiO₂, and is so formulatedthat when heated above a certain temperature (as during the firing ofthe ceramic body) fine grained diopside crystals precipitate out and actas a flux, lowering the firing temperature substantially, for example,at least three Seger cones as compared to the firing temperature thatwould be required without the diopside crystals. The frit containsleachable deflocculent oxides which counterbalance any flocculentalkaline earths leached therefrom and prevent thickening of the slip toan unworkable viscosity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the present invention, a glass frit containing insolution the diopside precursors CaO, MgO, and SiO₂, is incorporatedwith a ceramic material that is shaped into a body and fired to achievethe desired degree of vitrification. During the firing, diopside formsfrom the precursors and precipitates as fine crystals which serve as aflux. The crystalline, fluxing diopside substantially lowers the firingtemperature required of the ceramic material in forming thesanitary-ware or other body.

Considering these components in greater detail, the diopside precursors,CaO, MgO, and SiO₂, should comprise at least 35% by weight of the glass.For example, such a glass may comprise in weight percent about:

CaO: 3.5 to 45.0

MgO: 2.5 to 30.0

SiO₂ : 30.0 to 78.0

Additive: 5.0 to 20.0

the additive being selected from one or more of the following inapproximately the percent indicated based on the total weight of theglass:

Li₂ O: 0 to 5

SrO: 0 to 5

ZnO: 0 to 5

K₂ O: 0 to 5

Na₂ O: 0 to 10

Al₂ O₃ : 0 to 12

ZrO₂ : 0 to 20

MoO₂ : 0 to 2

PbO: 0 to 5

B₂ O₃ : 0 to 5

CeO₂ : 0 to 2

P₂ O₅ : 0 to 4

F: 0 to 10

the fluorine when present being introduced into the batch as a fluorideof at least one metal of the composition.

A more desirable composition comprises in weight percent about:

CaO: 15 to 25

MgO: 10 to 20

SiO₂ : 35 to 50

Additive: 5 to 20

the additive being selected from one or more of the following inapproximately the percent indicated based on the total weight of theglass:

K₂ O:0 to 5

Na₂ O: 0 to 10

Li₂ O: 0 to 5

P₂ O₅ : 0 to 4

Al₂ O₃ : 0 to 12

B₂ O₃ : 0 to 5

A preferred compositional range and a preferred composition for theglass containing the diopside precursors are in weight percent about:

    ______________________________________                                        Ingredient    Range      Percentage                                           ______________________________________                                        CaO           3.5 to 40.3                                                                              22.1                                                 MgO           2.6 to 26.0                                                                              18.4                                                 SiO.sub.2     30.0 to 76.3                                                                             46.0                                                 Al.sub.2 O.sub.3                                                                            5.0 to 12.0                                                                              9.25                                                 K.sub.2 O      0 to 2.3  1.4                                                  Na.sub.2 O     0 to 4.6  2.5                                                  Li.sub.2 O     0 to 0.2  0.1                                                  ______________________________________                                    

Depending upon the solubility characteristics of a given glass withinthe above range in a given slip, B₂ O₃ and/or P₂ O₅ could be added inweight percent amounts from 0 to 5 and 0 to 4 respectively.

It will be appreciated that these compositions constitute metal oxideanalyses of the smelted glass. The corresponding batch materials mayconstitute those materials which on smelting and cooling yield the oxideanalysis. For example, the present glasses can be smelted from dolomiteand lithospar in a weight ratio of about 76:24 to 11:89, respectively.Whiting can be substituted for a relatively small portion of thedolomite, and any of the other ingredients optionally included can beadded to the batch, either in the oxide or salt form or in a form whichreduces to the metal oxide or fluoride form on smelting. For example,spodumene, lepidolite, and the like may constitute part of the batchformulation.

Compositions with the ranges disclosed melt at temperaturesapproximating about 2600° F. to about 2750° F. The melt may be frittedin any convenient manner, such as by quenching the melt in water orpassing it between fritting rollers. The frit so obtained isconventionally ground prior to use. As an example, the frit may beground so that about 95% passes through 325 mesh, U.S. Standard Sieve.X-ray examination shows that the frit is totally vitreous or nearly so.

A glass of the type described, containing the diopside precursors, isincorporated with suitable ceramic material that is adapted to formsanitary ware, and the mixture is then shaped into a body, as by slipcasting. The body is then fired to yield the sanitary ware. As describedmore fully hereinafter, the present glass does not significantly affectthe casting properties of the slip, and its viscosity may be controlledby providing counteracting or counterbalancing leachable amounts ofdeflocculent. In contrast other commercial glasses can markedly affectslip properties in a deleterious way.

A preferred ceramic material used to form the body is a feldspathic one,that is, bodies in which a substantial portion of the mineral content isfeldspar.

In accordance with the present invention, the temperature of firing islower by at least three Seger cones than would be required without thepresence of the instant glasses. Any addition of a present glass effectssome reduction in the firing temperature of the ceramic body. Amounts aslittle as 0.1% by weight of the body to as much as 10% or more areuseful. However, the preferred range of the glass is about 3% to about5% by weight of the ceramic body.

Upon firing a ceramic body containing a present glass, the describedprecursors precipitate in situ in the body as very fine crystals ofdiopside. In one instance, it was observed that the glass crystallizedat about 1652° F. (900° C.), although this temperature is not critical.Upon crystallization, at least about 50% by weight of the instant glassconverts to crystalline diopside, the balance forming a glassy residue.

The crystals formed are extremely fine and this is believed to be quiteadvantageous. A substantial portion of the crystalline diopside formedhas an average particle size less than one micron. Diopside formed inaccordance with the present invention is a better body flux thansynthetic diopside. This is believed to be due at least in part to thefine grained nature of the diopside formed which leads to fasterdissolution in the subsequent fluxing action. This fluxing actionaccorded by the present glasses is so effective that it lowers therequired firing temperatures at least three Seger pyrometric cones andtypically from cone 10 to 12 to cone 5 to 6, while still retaining agood, sufficiently wide firing temperature and reducing warpage.

X-ray diffraction results from fired mixtures of the present glasseswith feldspathic bodies show that no new compounds are formed other thanthe diopside crystals. A progressive glass formation appears to takeplace by fusion of the feldspathic matrix and assimilation of thediopside crystals.

For purposes of comparing the benefits and degree of utility of thepresent invention with that which has been practiced in the past, thefollowing is exemplary of a conventional cone 9-10 body composition usedheretofore:

    ______________________________________                                        Cone 9-10 Body Composition                                                                        Weight %                                                  ______________________________________                                        Plastic Ball Clay   34.0                                                      Kaolin              16.0                                                      Flint (200 Mesh)    18.0                                                      Feldspar            32.0                                                                          100.0                                                     Water               37.5                                                      Na.sub.2 SiO.sub.3  As required                                               ______________________________________                                    

The composition of the feldspar was essentially KNaO.Al₂ O₃.6SiO₂.

The sodium silicate was added as a 50% aqueous solution sufficient toachieve an initial slip viscosity as measured on a Brookfieldviscosimeter on either a #3 or a #5 spindle at 10 RPM.

The foregoing sanitary-ware body composition was cast into test barshaving the dimension one cm. by one cm. by 10 cm., and measured forfiring and total shrinkage, absorption and warpage, the results, fromcone 8 to cone 11, tabulated below in Table I.

                  TABLE I                                                         ______________________________________                                        Firing    % Firing                   % Total                                  Temperature                                                                             Shrinkage Absorption                                                                              Warpage                                                                              Shrinkage                                ______________________________________                                        Cone 8.sup.D 9.sup.2 -                                                                  9.35%     0.62%     0.021" 11.85%                                   Cone 9.sup.D 10.sup.1                                                                   9.53%     0.03%     0.022" 12.03%                                   Cone 10.sup.D 11.sup.1                                                                  9.59%     0.01%     0.030" 12.09%                                   Cone 11.sup.D 12.sup.1                                                                  9.17%     0.27%     0.033" 11.67%                                   ______________________________________                                    

The foregoing physical characteristics, as well as those which arereported in the following tables, were arrived at as follows:

Percentage Firing Shrinkage

This was determined as being the difference between dried length andfired length, divided by the dried length and multiplied by 100 toprovide the indicated percentage.

In this regard it should be noted that, at least theoretically andpredictably, the lower the shrinkage, generally the better.

However, because existing commercial molds have been designed to providea finished article in contemplation of 10% shrinkage, the body asdescribed below, utilizing the instant invention, has been compounded toprovide approximately 10% shrinkage to eliminate the need for extensivecommercial mold redesign at this time.

Percentage Absorption

Percentage absorption was obtained using ASTM test method C373-72.

An absorption of approximately 0.5% or less is generally necessary toassure a sufficiently vitrified body. Considering the use to whichsanitary ware is put, and further considering that not every square inchof surface exposed to water will be glazed, the need for a high degreeof vitrification will be readily apparent.

Warpage

Warpage was measured on test bars supported over a five inch span duringfiring, the measurement, after cooling to room temperature, taken twoand one half inches from either support at the midpoint, using a depthgauge, the droop being taken as a measure of the degree of warpage,reported in inches.

A warpage of 20 mils, slightly more or less, is considered to be aboutthe norm, and would be expected to produce commercially acceptable ware.Anything materially beyond 20 mils would likely result in commerciallyunacceptable fixtures.

Percent Total Shrinkage

This figure was determined essentially the same as firing shrinkage,except the initial measurement was made while the test bar was still inthe plastic state, prior to drying.

Modulus of Rupture

Modulus of Rupture was calculated using the standard formula:

    M=3P1/2bd.sup.2

where

M=the modulus of rupture in pounds per square inch;

P=the breaking load, in pounds;

l=the distance between the knife edges in inches;

b=the breadth of the bar in inches;

d=the depth of the bar in inches.

Modulus of rupture of course is a measure of the strength of the firedbody. Commercial sanitary ware under our experimental conditions yieldsmodulus of rupture values of about 7000 pounds per square inch, and thismay be compared with experimental body values shown in Table IV.

To comparatively demonstrate the effectiveness of the instant inventionin substantially lowering both the firing temperature, as well as thetime of firing of a sanitary-ware body, the following cone 5-6 base bodycomposition was used:

    ______________________________________                                        Cone 5-6 Base Body Composition                                                                    Parts by Weight                                           ______________________________________                                        Plastic Ball Clay   34.0                                                      Kaolin              16.0                                                      Flint (200 Mesh)    12.5                                                      Feldspar            32.5                                                                          95.0                                                      (Na.sub.2 SiO.sub.3 and water as nesessary)                                   ______________________________________                                    

It will be seen that, but for a slight reduction in SiO₂, the above basebody composition is essentially the same as that set forth above forcone 9-10 processing.

Using the cone 5-6 base composition as just given as the feldspathicbody, there is tabulated in the following Table II the components of aseries of sanitary-ware slips which were weighed and mixed with variousauxiliary components added as noted and the viscosity, as with the cone9 body, adjusted with a 50% solution of Na₂ SiO₃.

                  TABLE II                                                        ______________________________________                                        Parts are by Weight                                                           ______________________________________                                        Body Compositions                                                                         1      2       3    4     5    6                                  ______________________________________                                        Base Composition                                                                          950    970     985  970   985  970                                Flux A      --     30      15   --    --   --                                 Flux B      --     --      --   30    15   --                                 Flux C      --     --      --   --    --   30                                             950    1000    1000 1000  1000 1000                               Water       375    375     375  375   375  375                                ______________________________________                                        Body Compositions                                                                         7      8      9    10   11   12   13                              ______________________________________                                        Base Composition                                                                          970    970    970  970  970  985  970                             Synthetic Diopside                                                                        30     15     --   --   --   --   --                              Residual Glass                                                                            --     15     --   --   --   --   15                              Calcined Dolomite                                                                         --     --     12   --   --   --   --                              Lithospar   --     --     17.5 8.7  --   --   --                              Dolomite    --     --     --   21.3 --   --   --                              Vitreous Diopside                                                                         --     --     --   --   30   15   15                                          1000   1000   1000 1000 1000 1000 1000                            Water       375    375    375  375  375  375  375                             ______________________________________                                    

Referring in more detail to the fluxes listed in Table II, Flux A was ahigh calcium, alumina silicate glass having a refractive index of 1.65.Flux B was a glass flux purchased on the open market and is understoodto comprise ground window glass having a coating to make the glassparticles more water resistant. Flux C was a glass of the presentinvention and comprised in weight percent:

    ______________________________________                                               SiO.sub.2                                                                             46.0                                                                  Al.sub.2 O.sub.3                                                                      9.25                                                                  CaO     22.1                                                                  MgO     18.4                                                                  Na.sub.2 O                                                                            2.5                                                                   K.sub.2 O                                                                             1.4                                                                   Impurities                                                                            0.35                                                                          100.00                                                         ______________________________________                                    

The flux indicated as residual glass comprised the composition justgiven minus the diopside precipitated therefrom. That is, the oxidesremaining in Flux C after the combination of some of the MgO, CaO andSiO₂ to give diopside crystals (50% by weight of the flux) were used asthe constituents of the residual glass flux. Body 13 would thus bechemically the same as body 6, though the oxides are combineddifferently. Bodies 9 and 10 were made to illustrate that the rawmaterials from which Flux C could be made by melting cannot be used assuch in the casting slip. Vitreous diopside was prepared by meltingdolomite and quartz in the proportions 184:120 by weight, respectively,to yield a composition containing MgO, CaO and SiO₂ in the proportionspresent in diopside and quenching to form a glass.

The following Table III lists the viscosity measurements for each bodycomposition set forth in Table II.

                  TABLE III                                                       ______________________________________                                        Stability of Slips of Table II                                                Brookfield Viscosity in Poises                                                Body   Na.sub.2 SiO.sub.3                                                     Compo- ml/Kg    Initial  Aged     Aged  Aged                                  sition of Slip  Visc.    1 Day    2 Days                                                                              3 Days                                ______________________________________                                        1      5        19.9     10.6      9.6   9.0                                  2      6.5      20.4     30.0     42.2  67.5                                  3      5.75     16.5     55.3     61.0  184.0                                                                         (#5 Spin-                                                                     dle)                                                                          1 ml                                                                          Na.sub.2 SiO.sub.3                    4      5.3      36.1     13.0     10.3   9.1                                  5      5.2      29.4     10.0      8.1   7.2                                  6      5.0      16.0     27.8                                                                          1 ml                                                                 Na.sub.2 SiO.sub.3                                                                     15.3     15.3  20.2                                  7      7.25     23.8     38.3     31.8  36.4                                  8      5.75     23.9     370.4                                                                         (#5 Spindle)                                                                  1.75 ml                                                                       Na.sub.2 SiO.sub.3                                                                     21.5   9.3                                  9      Addition of calcined dolomite set the slip up and                             it could not be deflocculated.                                         10     After one day slip was too viscous to remove from                             container.                                                             11     5        26.1     Too viscous to remove                                                         from container.                                      12     5        18.0     Too viscous to remove                                                         from container.                                      13     5        16.5     Too viscous to remove                                                         from container.                                      14     4        19.0     10.9     --    12.2                                  ______________________________________                                    

Body composition 14 in Tables III and IV represents the cone 9-10 bodycomposition previously given. The sodium silicate was added to the slipsto deflocculate the clay. The Brookfield viscosities were determinedwith No. 3 Spindle at 10 rpm. except for Body Compositions 3 and 8 whereNo. 5 Spindle was used with additional sodium silicate as indicated by alower entry line for late aging periods for those compositions.Similarly, an added amount of sodium silicate was used for BodyComposition 6 for testing at the aging level of two days and more.

Referring to Table III, Body Compositions 1 and 14 show the normalgradual reduction of viscosity with age. Body Compositions 2 and 3 withFlux A required more sodium silicate for initial deflocculation than didBody Composition 6 containing a flux of the present invention. BodyCompositions containing Flux A also showed a thickening tendency onaging. Similarly, the synthetic diopside required more sodium silicatefor initial deflocculation than the present Body Composition 6, and theviscosity of the former increased with age. When calcined dolomite wasadded, the slip, thickened to a thick paste and it was not possible todeflocculate it (Body 7). Body compositions 10, 11, 12 and 13 all causedtheir respective slips to thicken to a stiff paste after one day.

Critical data from the standpoint of the finished, fired piece, are setforth in Table IV. Only Body Compositions 2, 4, 6 and 7 even approachedvitrification at a temperature of cone 6. Body Compositions 11, 12 and13 thickened very rapidly on aging and were impractical for use in acasting slip. Of the remaining compositions, only Body Compositions 6and 7 gave lower absorptions.

                                      TABLE IV                                    __________________________________________________________________________    Results of Fired Body Compositions                                            Body Composition                                                                       1  2  3  4  5  6  7  8  9  10 11 12 13 14                            __________________________________________________________________________    % Firing                                                                      Shrinkage                                                                     Cone 4.sup.D 5.sup.1                                                                   7.1                                                                              7.1                                                                              6.7                                                                              8.7                                                                              6.7                                                                              9.1                                                                              9.5                                                                              9.4                                                                              -- 7.5                                                                              9.6                                                                              8.8                                                                              9.9                                                                              7.2                           Cone 5.sup.D 6.sup.1                                                                   8.1                                                                              8.5                                                                              8.8                                                                              9.4                                                                              8.1                                                                              9.9                                                                              9.8                                                                              9.8                                                                              -- 8.4                                                                              10.2                                                                             9.7                                                                              9.9                                                                              7.9                           Cone 6.sup.D 7.sup.1                                                                   8.6                                                                              8.9                                                                              8.9                                                                              9.5                                                                              8.5                                                                              10.1                                                                             10.3                                                                             9.8                                                                              -- 8.2                                                                              10.4                                                                             10.3                                                                             10.0                                                                             8.3                           % Absorption                                                                  Cone 4.sup.D 5.sup.1                                                                   4.8                                                                              4.0                                                                              4.1                                                                              3.5                                                                              3.7                                                                              2.8                                                                              2.8                                                                              2.9                                                                              -- 4.9                                                                              2.6                                                                              3.0                                                                              2.3                                                                              5.3                           Cone 5.sup.D 6.sup.1                                                                   3.5                                                                              1.8                                                                              3.3                                                                              2.1                                                                              3.2                                                                              0.8                                                                              0.8                                                                              1.0                                                                              -- 2.9                                                                              0.3                                                                              1.4                                                                              0.4                                                                              4.2                           Cone 6.sup.D 7.sup.1                                                                   2.7                                                                              0.8                                                                              1.5                                                                              0.7                                                                              2.2                                                                              0.3                                                                              0.3                                                                              0.2                                                                              -- 2.2                                                                              0.1                                                                              0.8                                                                              0.2                                                                              3.2                           Warpage                                                                       Cone 4.sup.D 5.sup.1                                                                   0.012                                                                            0.012                                                                            0.011                                                                            0.016                                                                            0.013                                                                            0.014                                                                            0.018                                                                            0.018                                                                            -- 0.011                                                                            0.014                                                                            0.014                                                                            0.013                                                                            0.008                         Cone 5.sup.D 6.sup.1                                                                   0.012                                                                            0.014                                                                            0.013                                                                            0.018                                                                            0.015                                                                            0.020                                                                            0.022                                                                            0.020                                                                            -- 0.016                                                                            0.025                                                                            0.019                                                                            0.027                                                                            0.013                         Cone 6.sup.D 7.sup.1                                                                   0.017                                                                            0.018                                                                            0.019                                                                            0.027                                                                            0.019                                                                            0.021                                                                            0.023                                                                            0.023                                                                            -- 0.019                                                                            0.024                                                                            0.025                                                                            0.032                                                                            0.015                         Modulus                                                                       of Rupture                                                                    Cone 4.sup.D 5.sup.1                                                                   5019                                                                             5133                                                                             4956                                                                             4070                                                                             3282                                                                             5246                                                                             5564                                                                             5510                                                                             -- 4032                                                                             5073                                                                             3407*                                                                            5418                                                                              --                           Cone 5.sup.D 6.sup.1                                                                   4904                                                                             4389                                                                             4538                                                                             5486                                                                             5424                                                                             6130                                                                             6274                                                                             5457                                                                             -- 5482                                                                             5878                                                                             5404                                                                             5351                                                                              --                           Cone 6.sup.D 7.sup.1                                                                   4957                                                                             5274                                                                             3973                                                                             5821                                                                             5389                                                                             7203                                                                             7150                                                                             6034                                                                             -- 4932                                                                             5162                                                                             2845*                                                                            5776                                                                              --                           __________________________________________________________________________     *Specimen cracked                                                        

It will be noted that when using the fritted source of dissolveddiopside in accordance with this invention as a body additive in theamounts set forth in Table II, the firing temperature was effectivelyreduced from cone 9-10 to cone 5-6. At the same time, the fired productsstill contained, in addition to relative ease of processing, thosecritical characteristics so essential to commercial success, namely,firing shrinkage, absorption, warpage, and modulus of rupture. Theseproperties are all well within the values required by the trade. It willalso be observed that other additives, even synthetic diopside, whenadded to the feldspathic body provided a number of serious drawbacks.The fluxing glasses of this invention have excellent properties in allcategories needed for fluxing action and are not outstanding in just afew of such categories.

Another aspect of the invention resides in balancing the deflocculentoxides and flocculent alkaline earths that are gradually leached fromthe fluxing glass frit when it is added to the ceramic slip. Suchbalancing imparts or improves slip stability, that is, it maintains theviscosity of the slip at workable viscosity values.

More particularly, as the alkaline earths are leached from the frit,they tend to raise the viscosity and even solidify the slip. But if thedeflocculent oxides are leached along with the flocculents, thedeflocculent oxides counterbalance or counteract the flocculents toprovide a stable, workable slip viscosity. Deflocculent oxides includeany metal oxide that may be made a component of the glass frit and whichcounteracts as described the flocculating action of the alkaline earths.Examples of these are the alkali metal oxides such as sodium oxide,potassium oxide, and lithium oxide. After leaching from the glass, thedeflocculent oxides are usually present in the slip as silicates such assodium silicate, potassium silicate, and lithium silicate.

The amount of deflocculent oxides needed in the glass frit depends onhow much flocculent alkaline earths are leachable from the glass.Normally, however, at least 5% by weight of the glass frit should bedeflocculent oxides. The amount leached for both the deflocculent oxidesand the flocculent alkaline earths may be in the parts per millionrange, although substantially larger concentrations are possible. Theabsolute amounts leachable for either the deflocculent oxides orflocculent alkaline earths are not so critical as is the circumstancethat the two alkaline materials be present in amounts sufficient tocounterbalance or counteract each other to the extent they arerespectively leached from the frit upon its dispersal in a ceramic slip.There results a buffer or neutralization-like effect by which thedeflocculent oxides successfully prevent the flocculent alkaline earthfrom so changing the viscosity of the slip that it becomes unworkable.The net result is even better than adding sodium silicate or the like tothe slip after the frit has been added and undergone some leaching awayof its solubilities. The present frit is able to maintain relativelyconstant rheological properties for days following milling, requiringthe addition of only minimal amounts of a deflocculent such as sodiumsilicate.

Considering the previous data more fully from the standpoint ofbalancing the deflocculent oxides and flocculent alkaline earths, BodyCompositions 11, 12 and 13 of Table II use vitreous diopside as a flux.The vitreous diopside was prepared by melting the oxides in correctproportions and roll-quenching to form clear, uncrystallized glasshaving no free (unreacted and undissolved alkaline earths. As shown byTable III, Body Compositions 11, 12 and 13 within one day were tooviscous to be removed from the container. Referring to Table IV, it willbe noted that the modulus of rupture for these Body Compositions areextremely poor compared, for example, to that value for Body Composition6 which embodies the present invention. Test bodies were made from thesecompositions immediately from the slip while initial viscosity was stillworkable.

Body Compositions 7 and 8 which comprise synthetic diopside alsocontained as a result unreacted alkaline earths. Body Compositions 7 and8 required more sodium silicate because of the free alkaline earthspresent, but once the effect of the alkaline earths was counteracted,the slip was quite stable as no additional leaching would be expected.

In contrast, Body Composition 6 representing the invention required onlya normal amount of deflocculent for initially making the casting slipand a slight addition after 24 hours, after which the slip was stable.

The following Table V provides seven additional examples of the presentglass composition from which frit can be made as described.

                  TABLE V                                                         ______________________________________                                        Exemplary Glass Compositions                                                  For The Present Frit                                                          Example                                                                              A       B      C     D    E    F    G    H                             ______________________________________                                        K.sub.2 O                                                                            1.4     1.4    1.5   1.4  1.4  1.4  1.52 1.54                          Na.sub.2 O                                                                           2.8     5.4    5.7   6.6  7.8  9.1  5.64 5.73                          Li.sub.2 O                                                                           0.1     0.1    0.1   0.1  0.1  0.1  1.17 1.19                          CaO    23.9    20.5   17.1  19.5 18.5 17.5 8.21 6.27                          MgO    17.8    15.2   12.6  14.5 13.7 13.0 5.91 4.45                          Al.sub.2 O.sub.3                                                                     6.7     6.7    7.4   6.8  6.8  6.9  11.15                                                                              11.32                         SiO.sub.2                                                                            47.3    47.3   52.1  47.6 48.2 48.4 59.96                                                                              60.92                         P.sub.2 O.sub.5                                                                      --      3.5    3.5   3.5  3.5  3.6  3.56 3.61                          B.sub.2 O.sub.3                                                                      --      --     --    --   --   --   2.88 4.98                          ______________________________________                                    

Extraction measurements were carried out on powders of Examples A and Bof Table V and, for comparison purposes, on the synthetic diopside,glass Flux B, and vitreous diopside of Table II. In each case, one gramof the flux powder having a particle size to pass all but 3% on 325Mesh, U.S. Standard Sieve, was shaken with 100 milliliters of distilledwater for 24 hours. The solution was then filtered and diluted to 250ml. The elements were estimated on the diluted portion by atomicabsorption. Table VI shows the results.

                  TABLE VI                                                        ______________________________________                                        Weight Percent                                                                Flux     Na.sup.+ K.sup.+                                                                              Ca.sup.++                                                                             Mg.sup.++                                                                            pH                                    ______________________________________                                        Example A                                                                              0.11     0.08   0.36    0.01   10.9                                  Example B                                                                              0.10     0.02   0.03    0.04    9.9                                  Synthetic                                                                              0.01     0.01   0.15    0.02   10.1                                  Diopside                                                                      Glass Flux B                                                                           0.24     0.03   0.04     0.006  8.2                                  Vitreous 0.02     0.01   0.33    0.02   10.3                                  Diopside                                                                      ______________________________________                                    

High Ca⁺⁺ extractions lead to thickening, while high Na⁺ leads tothinning of the slip. Example A has both high Ca⁺⁺ and reasonably highNa⁺, so that its behavior is that of a composite. It does thicken theslip somewhat but nowhere nearly as badly as vitreous diopside does.Example B contains more Na₂ O than Example A to enhance or maintain Na⁺extractability. Table VI indicates that the Ca⁺⁺ extraction from ExampleB into solution has indeed been drastically reduced, while the Na⁺ hasnot been affected.

The glass compositions of Table V are detailed in Table VII with respectto extraction and slip stability.

All casting slips of Table VII have good viscosity stability. The sametechnique described for Table VI was used in determining the elementalconcentrations in weight percent. The casting slip used was the same mixas in Table II, using a three weight percent flux glass, but in addition1.5 grams of soda ash were added per kilogram of body. All cast bodiesusing these flux glasses were fired to less than 1% porosity at Segercone 5. There are differences in the physical conditions of the bodiescast as the glass flux is changed. For instance, the properties maychange in hardness to softness, ease of trimming, brittleness toplasticity, and the like. These factors would be factors to consider inselecting a particular glass composition for use with any particularindustrial body composition mix. The present invention does, therefore,provide flexibility in the glass composition that may be used withoutlosing slip stability and the usefulness of the composition as a bodyflux.

While the preferred embodiment hereof is represented by a slip castsanitary-ware body, as will be understood by those skilled in the art,the benefits of the present invention, though perhaps not as pronouncedor dramatic as they appear in a sanitary-ware body, would quite likelybe applicable to any fired, ceramic body; would definitely be applicableto any body which could be characterized by those skilled in thisparticular art, as a "feldspathic" body.

And, while the preferred embodiment hereof involves slip castsanitary-ware, other than as slip solubility benefits are aconsideration, the method of forming the body, whether by extrusion, drypressing, etc., would have no bearing on the final results achieved, andas such, method of forming really forms no limiting feature of theinvention disclosed herein.

                                      TABLE VII                                   __________________________________________________________________________    Properties of Glass Fluxes of Table V                                                                         Brookfield Viscosity #3 Spindle               Weight Percent                  POISES                                         Extractabilities        ml Sodium                                                                            Ready for         Condition                   Example                                                                            Na.sup.+                                                                         K.sup.+                                                                          Ca.sup.++                                                                         Mg.sup.++                                                                         P.sup.5+                                                                         pH Silicate Used                                                                        Casting                                                                             1 Day                                                                             2 Days                                                                            5 Days                                                                            of Cast                     __________________________________________________________________________    A    0.11                                                                             0.08                                                                             0.36                                                                              0.01                                                                               --                                                                              10.9                                                                             --     --    --  --  --  --                          B    0.10                                                                             0.02                                                                             0.03                                                                              0.04                                                                              0.02                                                                             9.9                                                                               4.25  15.0  12.0                                                                              13.5                                                                              16.5                                                                              Brittle                     C    0.07                                                                             0.02                                                                             0.02                                                                              0.04                                                                              0.01                                                                             9.4                                                                               2.15  12.0  14.5                                                                              15.0                                                                              22.5                                                                              Brittle                     D    0.08                                                                             0.02                                                                             0.02                                                                              0.03                                                                              0.02                                                                             9.8                                                                              3.9    13.0  13.5                                                                              14.5                                                                              16.5                                                                              Fair                        E    0.11                                                                             0.02                                                                             0.05                                                                              0.05                                                                              0.007                                                                            9.6                                                                               2.95  13.0  13.5                                                                              14.5                                                                              19.5                                                                              Fair                        F    0.10                                                                             0.02                                                                             0.01                                                                              0.04                                                                              0.03                                                                             9.6                                                                              2.5    12.5  14.0                                                                              15.5                                                                              22.0                                                                              Best of                                                                       Series                       D*  0.04                                                                             0.006                                                                            0.05                                                                              0.03                                                                              0.008                                                                            10.0                                                                             4.4    11.8   9.4                                                                               8.9                                                                               8.0                                                                              Good                        G    0.04                                                                             0.006                                                                            0.04                                                                              0.02                                                                              0.02                                                                             9.8                                                                              4.9    12.8   8.2                                                                               8.2                                                                               6.9                                                                              Good                        H    0.04                                                                             0.005                                                                            0.04                                                                              0.02                                                                              0.03                                                                             9.9                                                                              3.6    11.4  14.9                                                                              12.4                                                                              11.0                                                                              Good                        __________________________________________________________________________     *This is the substantial equivalent of D above, run as a standard over a      year later for comparison with newly added Examples G and H.             

The examples hereof amply demonstrate that the fine-grained diopsidecrystals of this invention lower the firing temperature of thefeldspathic body disclosed by at least three Seger cones.

Obviously however, an amount of the crystals and/or frit of thisinvention which would promote any measurable reduction in firingtemperature and/or time of a ceramic body would constitute a "fluxingamount." Certainly, lowering the required heat treatment even one Segercone would involve a "fluxing amount" of the diopside crystals and/orglass of this invention.

Although the foregoing describes several embodiments of the presentinvention, it is understood that the invention may be practiced in stillother forms within the scope of the following claims.

I claim:
 1. A substantially completely vitreous, smelted, clear glassfrit containing:(a) leachable amounts of deflocculent oxides andflocculent alkaline earths and adapted to serve as a ceramic body fluxin a ceramic slip without thickening the slip to an unworkableviscosity, (b) said frit being completely liquid at a smeltingtemperature of about 2600° F. to about 2750° F. and containing insolution the diopside precursors CaO, MgO, and SiO₂, said fritconsisting essentially of the following components, said diopsideprecursors comprising at least 35% by weight of said frit:CaO: 6.27 to23.9 MgO: 4.45 to 18.4 SiO₂ : 46.0 to 60.92 Additive: 5 to 20saidadditive being selected from one or more of the following inapproximately the percent indicated based on the total weight of theglass: K₂ O: 1.4 to 1.54 Na₂ O: 2.5 to 9.1 Li₂ O: 0.1 to 1.19 Al₂ O₃ :6.7 to 11.32 (c) said frit being adapted upon heating to crystallizefrom solution at least a fluxing amount of said precursors in the formof fine diopside crystals having an average particle size less than onemicron and being substantially free of unreacted alkaline earths, and(d) said deflocculent oxides and flocculent alkaline earths beingleachable from said frit in sufficient relative amounts tocounterbalance each other and prevent said thickening of the slip to anunworkable viscosity, and (e) the foregoing composition containingadditionallyB₂ O₃ : 2.88 to 4.98 P₂ O₅ : 3.5 to 3.61
 2. The glass fritof claim 1 in which at least 50% by weight of said diopside precursorsare converted to said diopside crystals during said heating.
 3. Theglass frit of claim 5 in which said heating is at a temperature fromabout Seger cone five (5) to about cone six (6).